Herbicidal anilinomethylene-malononitriles

ABSTRACT

HERBICIDAL ANILINOMETHYLENEMALONOTRILE COMPOUNDS OF THE FORMULA   (2-A1,3-A2,4-A3,5-A4,6-A5-PHENYL)-N(-R1)-CH=C(-CN)2   WHEREIN R1 IS SELECTED FROM THE GROUP CONSISTING OF HYDROGEN, ALKYL HAVING A MAXIMUM OF 8 CARBON ATOMS AND THE GROUP   -CO-R   IN WHICH R IS AN ALKYL, A1, A2, A3, A4, AND A5 ARE INDEPENDENTLY SELECTED FROM THE GROUP CONSISTING OF HYDROGEN, ALKYL, HALOGEN, HALOALKYL, NITRO, CYANO, HYDROXY, ALKOXY, PHENOXY, PHENYL AND SUBSTITUTED PHENYL.

United States Patent 3,726,662 HERBICIDAL ANILINOMETHYLENE- MALONONITRILES Robert K. Howe, Bridgeton, and Joseph W. Baker, Kirk- ;Iood, Mo., assignors to Monsanto Company, St. Louis,

No Drawing. Filed Jan. 14, 1970, Ser. No. 2,961 The portion of the term of the patent subsequent to Dec. 29, 1987, has been disclaimed Int. Cl. A01n 9/20 US. Cl. 71-103 6 Claims ABSTRACT OF THE DISCLOSURE Herbicidal anilinomethylenemalononitrile compounds of the formula wherein R is selected from the group consisting of hydrogen, alkyl having a maximum of 8 carbon atoms and the group in which R is an alkyl; A A A A and A are independently selected from the group consisting of hydrogen, alkyl, halogen, haloalkyl, nitro, cyano, hydroxy, alkoxy, phenoxy, phenyl and substituted phenyl.

Herbicidal anilinomethylenemalononitriles i, i, wherein R is selected from the group consisting of hydrogen, alkyl having a maximum of 8 carbon atoms and the group in which R is an alkyl of a maximum of 4 carbon atoms; A A A A and A are independently selected from the group consisting of hydrogen, alkyl having a maximum of 8 carbon atoms, halogen (i.e. chlorine, bromine, fluorine, iodine), haloalkyl of a maximum of 8 carbon atoms, nitro, cyano, hydroxy, alkoxy of a maximum of 5 carbon atoms, phenoxy, carboalkoxy of a maximum of 8 carbon atoms,

3,726,662 Patented Apr. 10, 1973 ice wherein R and R are alkyl groups of a maximum of 5 carbon atoms, phenyl and substituted phenyl in which the substituents are the other groups defined by A A A3, A4 and A5- The preferred anilinomethylenemalononitrile compounds of this invention are represented by the formula R2 ON R 1 CN wherein R is selected from the group consisting of hydrogen, alkyl of a maximum of 8 carbon atoms and the group where R is an alkyl of a maximum of 4 carbon atoms; R R and R are each independently selected from the group consisting of hydrogen, alkyl of a maximum of 8 carbon atoms, hydroxy, alkoxy of a maximum of 5 carbon atoms, phenoxy, halogen, haloalkyl of a maximum of 8 carbon atoms, nitro, carboalkoxy of a maximum of 5 carbon atoms,

and at least one of R R and R are methyl, halogen or halomethyl. The most preferred compounds of this group of compounds are those containing substituents in the meta or 3 position and especially in both meta positions or the 3 and 5 positions.

R is hydrogen and R R and R are selected from the group consisting of hydrogen, halogen, methyl, halomethyl, nitro and methoxy with the provision that at least two or R R and R are other than hydrogen. The most preferred compounds of this group of compounds are those containing substituents in the meta or 3 position and especially in both meta positions or the 3 and 5 positions.

The term herbicide as used herein and in the appended claims means materials which (1) effectively control the growth of all plants in a given locus or (2) selectively control the growth of one or more plant species in the presence of other plants.

The term control as used herein and in the appended claims is inclusive of the actions of (1) killing, (2) inhibiting growth, reproduction or proliferation, and (3) removing, destroying or otherwise diminishing the occurrence and activity of plans and is applicable to any of the stated actions, or any combination thereof.

The herbicides herein defined are suitable for controlling the growth of plants in pre-emergent and post-emergent plant applications. That is, they are effective in controlling the growth of dormant seeds, germinant seeds, germinative seeds, emerging seedlings and established woody and herbaceous vegetation by exposing the seeds, emerging seedlings, or the roots or above-ground portions to the action of an effective amount of one or more of said anilinomethylenemalononitriles. However, the best results are obtained with the compounds of this invention in a post-emergence situation by spraying the compounds on the plants.-

For the sake of brevity and simplicity, the term active ingredient is used hereinafter in the specification to describe the anilinomethylenemalononitrile compositions of this invention.

In foliar treatment for the modification of vegetative growth, the active ingredients are applied in amounts from about 0.1 to about 25 or more pounds per acre. In applications to soil for the modification of the growth of germinant seeds, germinative seeds, emerging seedlings and established vegetation, the active ingredients are applied in'amounts from about 1 to about 50 or more pounds per acre. In such soil applications, it is desirable that the active ingredients be distributed to a depth of at least 0.2 inch. In selective pre-emergence herbicide applications the active ingredients are usually applied in amounts from about I to 50 pounds per acre but preferably from about I to pounds per acre. It is believed that one skilled in the art can readily determine from the teachings of this specification, including the examples herein, the general procedure for any application.

The preparation of the various anilinomethylenemalononitriles of this invention is by known methods and in most cases consists in the reaction of the appropriate amine with ethoxymethylenemalononitrile as follows:

l l CN wherein R A A A A, and A are as previously defined.

Reactions of substituted anilines with alkoxymethylenemalononitriles are usually run at a temperature in the approximate range of about 10150 C. The compounds are preferably dissolved in a suitable solvent including lower alkyl ethers and alcohols, such as diethyl ether, methanol, propanol and the like, and aromatic hydrocarbons such as benzene, toluene and the like. The reaction mixture is normally heated to the reflux temperature of the mixture and maintained at this temperature until the reaction is completed. The product is separated from the reaction mixture by conventional methods such as filtration, distillation, concentration and the like.

Having now described many ramifications and embodiments of the present invention, it is believed that an understanding thereof will be facilitated and made more full by the following examples. In these examples, as well as in the specification and appended claims, parts and percentages are by weight unless otherwise indicated.

EXAMPLE 1 To a suitable vessel equipped with an agitator, reflux condenser and thermometer was charged 22.9 parts (0.10 mole) of 3,5-di(trifluoromethyl)aniline and 12.2 parts (0.10 mole) of ethoxymethylenemalononitrile in 75 ml. ethanol and the mixture refluxed for 62 hours. The solution was then cooled, precipitating the product. The product was collected and washed with ethanol. Recrystallization from ethanol gave the product having a melting point A A of 234-236 C.

4 5 CN Analysis.Calculated for C I-I F N (percent): C,

47.22; H, 1.65. Found (percent): C, 47.44; H, 1.62. I CH5OCHHC\ 40 Illustrative examples of other anilinomethylenemalono- A A B1 CN nitrile compounds which were prepared (and in many 2 1 cases their physical properties) are given in Table 1.

TABLE I /CN 113- III-011:0

i 1 R1 ON A2 1 Melting;

01!! A1 A2 A3 A4 A5 0.)

H H H H H 255-257 H H H H H 115-117 H CHaO H H 268-270 H CH3O H H H 198-200 Cl H H H H 148. 15-151. 5 H 01 H H H 201-202 H CF H H H 228-229 H H CF3 H H 275-276 H H N02 H H 318-319 CH H H H H 162. 5-164. 5 H H or H H a 290-291 H H C H H H 234-235 H H C O O C2115 H H 239-241 H H COOC2H5 H H 126-128 H H COOCzHs H H 159-170 H CH3 H H H 184-196 H CH3 H H H 101-103 H CH3 H H H 39-40 H C1 01 H H 269-270 H C1 01 H H o' H H CF 01 H H 237-239 H H N03 01 H H 238-239 H H CH CH3 H H 222-224 H 01 H t-C1H1 H H 188-190 H CH; 01 H H H 186-189 CH; H CF; 01 H H 93-95 H H CF; H OF; H 233-235 H H OF; H H Cl 177-179 H CH3 H H H CH3 I 170-172 H H OF; H H Br 157-159 CH3 H OF; H Fa H -142 CH H CF; H H 01 10a. 5-108 H 01 H 01 H H 240-242 35 C Hs H Cl Cl H H 89430 See footnotes at end of table,

TAB LE I-Gontinued Melting point A1 A2 A A A5 C.)

Cl H Cl H H 127-128 Cl H Cl H H 110-111 H Cl Cl H H 159-162 Cl Cl H H H 140-142 Cl H H Cl H 107-111 Cl Cl H H H 77-78 Cl H H Cl H 49-55 H CF H CF; H 118-120 Cl H H Cl H I 189-191 Cl Cl H H H 194-196 H Cl CH3 H H 222-224 H Cl CH3 H H 142-144 H Cl CH H H 99-102 H C IF; C1 H H 68-75 CI H C1 C1 H B 243-245 CH H Br Cl H 231-232 H C1 3 B r H Br 225-227. 5

H H H H H 171-173 O C N (C H3) 2 54 H H H H H H 197-198 0 O NH O H3 55 H H (H H H H 243-244 NHC-O-CH (CHa)2 H H NHzSOz H H 238-242 0 C H H H C H3 H 216-219 C H H H N O 2 H 178-180 N O g H H H 224-227 0 H H H H H 192-193 Cl H Cl H 261-263 H O(]%NHC (CHM! H H H 200-201 Cl C 113 H H 139-141 0 H H H H 94-95 H Cl H H 155-156 C l H Cl H 88-90 01 H Cl H 145-147 Cl H Cl H 93-95 H C1 C1 H 158-159 H H H C H3 131-132 H H H C Ha 120-121 H H H H 70-72 H CH H H 286-289 H (I? H H 303-305 NH C -C H3 75.. C2H 01 H C1 C1 H 101-103 76 C 2H Cl H H C F: H 73-73 77 CaH1 H C1 C1 H H 70-72 781 CaH1 H CF; H CF H 68- 79 A H CH H CH3 H 215-217 s0 C4H9 H CF: H CFs H 81 CH(CH H Cl H Cl H 132-133 g2 2 5 H C H H C H; H 73-75 83 H Cl H H C F H 177-179 84 H BI H H 0 Fa H 157-159 B Decomposition.

CH3 C 3 b CgHn=CH -dlCH2-Cl1 C H CH EXAMPLE 85 approximately 14 days and the results recorded. The her- The pre-emergent herbicidal activity of the active ingredients of this invention is demonstrated as follows: A good grade of top soil is placed in aluminum pans and compacted to a depth of /s to /2" from the top of each pan. A predetermined number of seeds of the test plant species are placed on top of the soil in the pans. The seeds are covered with a /6" layer of soil and the pan leveled. The active ingredient is applied by spraying the surface of the top layer of soil with a herbicidal formulation containing a suflicient amount of active ingredient to obtain the desired rate of active ingredient per acre. For soil incorporation, the chemical is sprayed on and mixed into the soil used to cover the seeds' The seed-containing pans are placed on a wet sand bench and maintained uder ordinary conditions of sunlight and watering. The plants are observed at the end of bicidal activity index is based on the average percent control of each seed lot. The herbicidal activity index is converted to a relative numerical scale for the sake of brevity and simplicity in the table.

The pre-etnergent herbicidal activity index used is defined as follows:

In Table 11 following, the aniliniomethylenernalononitrile compound, the dosage rate, method of application, the spectrum of plant seeds treated, and the results of the tests carried out according to the above procedure are indicated.

EXAMPLE 86 In a post-emergent herbicidal test, the active ingredients in each case is applied in spray form to 2 or 3 week old specimens of the plants (species indicated hereinafter). The herbicidal sprays are either wettable powder formulations or organic solvent-water solutions containing a surface active agent and varying amounts of the active ingredient. The solutions are applied to the plants in different pans at rates equal to the desired rate of active ingredient on a per acre basis. The treated plants are placed in a greenhouse and the effects are observed and recorded after approximately 14 days.

The post-emergent herbicidal activity index used in this example is defined as follows:

Numerical scale: Herbicidal activity No phytotoxicity.

1 Slight phytotoxicity.

2 Moderate phytotoxicity. 3 Severe phytotoxicity.

4 Plants dead.

In Table III the anilinomethylenemalononitrile compound, dosage rate, the spectrum of plants treated and the results obtained by the above procedure are indicated.

In practicing the herbicidal methods of this invention, the active ingredients can be used alone or in combination with a material referred to in the art as an adjuvant in liquid or solid form. Herbicidal formulations are prepared by admixing the active ingredient with an adjuvant which includes diluents, extenders, carriers and conditioning agents, the latter of which are surface active agents (or as some prefer, surfactants) to provide compositions in the form of finely-divided particulate solids, granules, pellets, solutions, dispersions or emulsions. Thus the active ingredient can be used with an adjuvant such as a finely-divided particulate solid, a liquid or organic origin, water, a wetting agent, a dispersing agent, an emulsifying agent or any suitable combination of these. The herbicidal formulations usually contain from about 0.01 percent to about 99 percent by weight of active ingredient.

Typical finely-divided solids which can be used with the active ingredients include the tales, natural and synthetic clays (e.g., kaolinites), fullers earth, salt, powdered wood, ground corn cobs, cottonseed hulls, wheat flour, and the like. Typical diluents include petroleum fractions such as kerosene, hexane, benzene, acetone, ethylene dichloride, Stoddard solvent, alcohols such as propanol and the like.

Specific surface-active agents which can be used in the herbicidal formulations of this invention are set out, for example, in Searle US. Patent 2,426,417, Todd US. Patent 2,655,447, Jones US. Patent 2,412,510 and Lenher US. Patent 2,139,276. A detailed list of such agents is also set forth by I. W. McCutcheon in Soap and Chemical Specialities, November 1947, page 8011 et seq., entitled Synthetic Detergents; Detergents and Emulsifiers-Up to Date (1960), by J. W. McCutcheon, Inc., and Bulletin 'E-607 of the Bureau of Entomology and Plant Quarantine of the USDA. In general, less than 50 parts by weight of the surface active agent is present per 100 parts by weight of herbicidal formulation.

Preferred wetting agents are alkyl benzene and alkyl naphthalene sulfonates, sulfated fatty alcohols, amines or acid amides, petroleum sulfonates, polyoxyethylene derivatives of alkylphenols (particularly isooctylphenol and nonylphenyl). Preferred dispersants are methyl cellulose, sodium naphthalene sulfonate, and sodium N- methyl-N-(long chain acid) taurates.

Wettable powder formulations usually contain from about 5 to about 95 parts by weight of active ingredient, from about 0.25 to 25 parts by weight of wetting agent, from about 0.25 to 25 parts by weight of dispersant and from 4.5 to about 94.5 parts by weight of inert solid extender, all parts being by weight of the total formulation. Where required from about 0.1 to 2.0 parts by weight of the solid inert extender can be replaced by a corrosion inhibitor or anti-foaming agent or both.

Dusts are dense finely-divided particulate formulations which are intended for application to the soil in dry form. Dusts contain primarily an active ingredient and a dense, free-flowing finely-divided particulate extender. However, their performance is sometimes aided by the inclusion of a wetting agent such as those listed hereinbefore. The dusts usually contain from about 0.5 to parts active ingredient, 0 to 50 parts wetting agent and 5 to 99.5 parts dense solid extender, all parts being by weight and based on the total weight of the dust.

The Wettable powders described above may also be used in the preparation of dusts, however, it is more advantageous to dilute them by blending with the dense dust diluent. In this manner, dispersing agents, corrosion inhibitors, and anti-foam agents may also be found as components of a dust.

Emulsifiable oil formulations are usually solutions of active ingredient in water-immiscible or partially waterimmiscible solvents together with a surface active agent. Suitable solvents for the active ingredient of this invention include hydrocarbons and water-immiscible ethers, esters or ketones. Suitable surfactants are found hereinabove. The emulsifiable oil formulations generally contain from about 5 to 95 parts active ingredient, about 1 to 50 parts surface active agent and about 4 to 94 parts solvent, all parts being by weight based on the total Weight of the emulsifiable oil.

Granules are physically stable particulate formulations comprising active ingredient adhering to or distributed through a basic matrix of an inert, finely-divided particulate extender. In order to aid leaching of the active ingredient from the particulate, a surface active agent such as those listed hereinbefore can be employed.

The mineral particles which are used in the herbicidal formulations usually have a size range of 10 to mesh, but preferably such that a large majority of the particles have from 14 to 60 mesh with the optimum size being from 20 to 40 mesh. Clay, having substantially all particles between 14 and 80 mesh and at least about 80 percent between 20 and 40 mesh, is particularly preferred to use in the herbicidal formulations. The term mesh as used herein means U.S. Sieve Series.

The granular herbicidal formulations generally contain from about 5 parts to about 30 parts by weight of active ingredient per 100 parts by weight of clay and 0 to about 5 parts by weight of surface active agent per 100 parts by weight of particulate clay. The preferred granular formulations contain from about 10 parts to about 25 parts by weight of active ingredient per 100 parts by weight of clay.

The herbicidal formulations can also contain other additaments; for example, fertilizers, other herbicides, plant growth regulants, pesticides and the like used as adjuvant or in combination with any of the above-described adjuvants.

While particuar embodiments of the invention have been described, it will be understood, of course, that the invention is not limited thereto, since many modifications may be made; and it is therefore contemplated to cover by the appended claims any such modifications as fall within the true spirit and scope of the invention.

What is claimed is:

1. Herbicidal method which comprises applying to plants a herbicidally effective amount of an anilinomethylenemalononitrile compound of the formula I /CN l l 1 ON A2 A1 11 wherein R is selected from the group consisting of hydrogen, alkyl having a maximum of 8 carbon atoms, and the group wherein R is an alkyl of a maximum of 4 carbon atoms; A A A A and A are independently selected from the group consisting of hydrogen, alkyl of a maximum of 8 carbon atoms, halogen, haloalkyl of a maximum of 8 carbon atoms, nitro, cyano, hydroxy, alkoxy of a maximum of 5 carbon atoms, phenoxy, carboalkoxy of a maximum of 8 carbon atoms,

NHm, OI('JN(R5)Z, NH%ORQ and NHzSOzwherein R and R are alkyl groups of a maximum of 5 carbon atoms, phenyl and substituted phenyl in which the substituents are the other groups defined in A A A A4 and A5.

2. Herbicidal method according to claim 1 wherein R is alkyl of a maximum of 8 carbon atoms.

3. Herbicidal method according to claim 2 wherein v 12' at least one of A A A A and A substituents is methyl halogen, or halomethyl and the remainder are hydrogen.

4. Herbicidal method according to claim 3 wherein at least one substituent is in a meta position.

5. Herbicidal method according to claim 2 wherein at least two of A A A A and A substituents are methyl, halogen or halomethyl, two of which are in meta positions and the remainder is hydrogen.

6. Herbicidal method according to claim 1 wherein said compound is applied to said plants subsequent to their emergence from the soil.

References Cited UNITED STATES PATENTS 3,213,124 10/1965 Sheppard 71-105 X 3,250,798 5/1966 Shulgin 71-405 X 3,551,573 12/1970 Baker et al. 260-4650 X JAMES O. THOMAS, JR., Primary Examiner Us. 01. X.R. 71 

